Supplementary Material (ESI) for Green Chemistry
This journal is (c) The Royal Society of Chemistry 2007

data_global
_journal_name_full               'Green Chemistry'

_journal_coden_Cambridge         1048

_publ_contact_author_name        'Zhiwei Miao'
_publ_contact_author_address     
;
Nankai Univeristy
Research Institute of Elemento-Organic Chemistry
Tianjin
300074
CHINA
;

_publ_contact_author_email       MIAOZHIWEI@NANKAI.EDU.CN

_publ_section_title              
;
Mannich type reaction of chlorophosphites,
phosphoramides and aldehydes (ketones) under solvent-free and
catalyst-free condition - Synthesis of N-phosphoramino
?-aminophosphonates
;
loop_
_publ_author_name
'Zhiwei Miao'
'Ruyu Chen'
'Zhanwei Cui'
'Yadan Wang'
'Fei Wang'
;
Jianfeng Zhang
;

data_shelxl
_database_code_depnum_ccdc_archive 'CCDC 645802'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C16 H27 N O7 P2'
_chemical_formula_sum            'C16 H27 N O7 P2'
_chemical_formula_weight         407.33

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   'P -1'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   9.955(9)
_cell_length_b                   10.404(9)
_cell_length_c                   10.839(9)
_cell_angle_alpha                97.689(9)
_cell_angle_beta                 98.771(7)
_cell_angle_gamma                111.382(16)
_cell_volume                     1011.0(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    113(2)
_cell_measurement_reflns_used    2306
_cell_measurement_theta_min      2.6
_cell_measurement_theta_max      25.0

_exptl_crystal_description       prism
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.08
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             432
_exptl_absorpt_coefficient_mu    0.251
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9657
_exptl_absorpt_correction_T_max  0.9802
_exptl_absorpt_process_details   'Jacobson, R. (1998) Private communication'

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      113(2)
_diffrn_radiation_wavelength     0.71070
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_monochromator  confocal
_diffrn_measurement_device_type  'Rigaku Saturn'
_diffrn_measurement_method       \w
_diffrn_detector_area_resol_mean 7.31
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            10348
_diffrn_reflns_av_R_equivalents  0.0440
_diffrn_reflns_av_sigmaI/netI    0.0540
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         1.94
_diffrn_reflns_theta_max         25.00
_reflns_number_total             3551
_reflns_number_gt                2931
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       CrystalClear
_computing_cell_refinement       CrystalClear
_computing_data_reduction        CrystalClear
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  'CrystalStructure 3.7.0'

_refine_special_details          
;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR and
goodness of fit S are based on F^2^, conventional R-factors R are based
on F, with F set to zero for negative F^2^. The threshold expression of
F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors based
on F^2^ are statistically about twice as large as those based on F, and R-
factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0632P)^2^+0.2781P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3551
_refine_ls_number_parameters     246
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0725
_refine_ls_R_factor_gt           0.0574
_refine_ls_wR_factor_ref         0.1388
_refine_ls_wR_factor_gt          0.1303
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_restrained_S_all      1.123
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
P1 P 0.32939(9) 0.40280(8) 0.15140(7) 0.0227(2) Uani 1 1 d . . .
P2 P 0.71709(9) 0.38095(8) 0.25502(7) 0.0226(2) Uani 1 1 d . . .
O1 O 0.3172(2) 0.4513(2) 0.03069(19) 0.0293(5) Uani 1 1 d . . .
O2 O 0.2109(2) 0.4188(2) 0.22605(18) 0.0246(5) Uani 1 1 d . . .
O3 O 0.3018(2) 0.2404(2) 0.12769(19) 0.0282(5) Uani 1 1 d . . .
O4 O 0.6432(2) 0.2840(2) 0.33408(18) 0.0248(5) Uani 1 1 d . . .
O5 O 0.8708(2) 0.4905(2) 0.33767(19) 0.0300(5) Uani 1 1 d . . .
O6 O 0.7647(2) 0.3160(2) 0.13907(19) 0.0292(5) Uani 1 1 d . . .
O7 O 0.4363(2) 0.6199(2) 0.4651(2) 0.0285(5) Uani 1 1 d . . .
H7 H 0.410(4) 0.660(4) 0.531(3) 0.043 Uiso 1 1 d . . .
N1 N 0.6169(3) 0.4596(3) 0.1943(2) 0.0224(6) Uani 1 1 d D . .
H1 H 0.633(3) 0.483(3) 0.1233(17) 0.034 Uiso 1 1 d D . .
C1 C 0.1680(3) 0.3334(3) 0.3214(3) 0.0282(7) Uani 1 1 d . . .
H1A H 0.0836 0.3469 0.3506 0.034 Uiso 1 1 calc R . .
H1B H 0.2515 0.3653 0.3962 0.034 Uiso 1 1 calc R . .
C2 C 0.1245(3) 0.1772(3) 0.2672(3) 0.0303(8) Uani 1 1 d . . .
C3 C 0.2568(4) 0.1598(3) 0.2254(3) 0.0326(8) Uani 1 1 d . . .
H3A H 0.3404 0.1920 0.3002 0.039 Uiso 1 1 calc R . .
H3B H 0.2314 0.0587 0.1914 0.039 Uiso 1 1 calc R . .
C4 C -0.0083(3) 0.1232(3) 0.1539(3) 0.0366(8) Uani 1 1 d . . .
H4A H 0.0200 0.1705 0.0839 0.055 Uiso 1 1 calc R . .
H4B H -0.0898 0.1434 0.1801 0.055 Uiso 1 1 calc R . .
H4C H -0.0401 0.0212 0.1252 0.055 Uiso 1 1 calc R . .
C5 C 0.0871(4) 0.0955(4) 0.3735(3) 0.0415(9) Uani 1 1 d . . .
H5A H 0.0674 -0.0039 0.3425 0.062 Uiso 1 1 calc R . .
H5B H -0.0007 0.1030 0.3987 0.062 Uiso 1 1 calc R . .
H5C H 0.1707 0.1352 0.4473 0.062 Uiso 1 1 calc R . .
C6 C 0.5107(3) 0.4962(3) 0.2565(3) 0.0217(7) Uani 1 1 d . . .
H6 H 0.5092 0.4603 0.3376 0.026 Uiso 1 1 calc R . .
C7 C 0.5487(3) 0.6543(3) 0.2891(3) 0.0215(6) Uani 1 1 d . . .
C8 C 0.5075(3) 0.7106(3) 0.3945(3) 0.0218(6) Uani 1 1 d . . .
C9 C 0.5409(3) 0.8550(3) 0.4259(3) 0.0282(7) Uani 1 1 d . . .
H9 H 0.5132 0.8924 0.4981 0.034 Uiso 1 1 calc R . .
C10 C 0.6148(3) 0.9446(3) 0.3512(3) 0.0296(7) Uani 1 1 d . . .
H10 H 0.6377 1.0429 0.3723 0.036 Uiso 1 1 calc R . .
C11 C 0.6545(3) 0.8891(3) 0.2463(3) 0.0315(8) Uani 1 1 d . . .
H11 H 0.7038 0.9495 0.1946 0.038 Uiso 1 1 calc R . .
C12 C 0.6228(3) 0.7452(3) 0.2159(3) 0.0256(7) Uani 1 1 d . . .
H12 H 0.6521 0.7086 0.1444 0.031 Uiso 1 1 calc R . .
C13 C 0.9665(4) 0.6004(4) 0.2836(4) 0.0533(11) Uani 1 1 d . . .
H13A H 0.9124 0.6564 0.2509 0.064 Uiso 1 1 calc R . .
H13B H 0.9966 0.5572 0.2114 0.064 Uiso 1 1 calc R . .
C14 C 1.0977(4) 0.6926(4) 0.3815(3) 0.0463(10) Uani 1 1 d . . .
H14A H 1.0675 0.7354 0.4526 0.070 Uiso 1 1 calc R . .
H14B H 1.1616 0.7670 0.3449 0.070 Uiso 1 1 calc R . .
H14C H 1.1520 0.6372 0.4124 0.070 Uiso 1 1 calc R . .
C15 C 0.6591(4) 0.2161(4) 0.0276(3) 0.0393(9) Uani 1 1 d . . .
H15A H 0.5696 0.2374 0.0102 0.047 Uiso 1 1 calc R . .
H15B H 0.6291 0.1188 0.0427 0.047 Uiso 1 1 calc R . .
C16 C 0.7334(5) 0.2299(5) -0.0839(3) 0.0540(11) Uani 1 1 d . . .
H16A H 0.7665 0.3276 -0.0955 0.081 Uiso 1 1 calc R . .
H16B H 0.6632 0.1670 -0.1613 0.081 Uiso 1 1 calc R . .
H16C H 0.8188 0.2040 -0.0674 0.081 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
P1 0.0254(5) 0.0250(4) 0.0228(4) 0.0079(3) 0.0114(3) 0.0122(3)
P2 0.0256(5) 0.0283(4) 0.0209(4) 0.0093(3) 0.0102(3) 0.0150(4)
O1 0.0335(13) 0.0400(13) 0.0213(11) 0.0150(10) 0.0127(9) 0.0168(11)
O2 0.0273(12) 0.0260(11) 0.0288(12) 0.0123(9) 0.0162(9) 0.0138(9)
O3 0.0309(12) 0.0218(11) 0.0353(13) 0.0067(10) 0.0148(10) 0.0110(9)
O4 0.0338(12) 0.0249(11) 0.0240(11) 0.0111(9) 0.0136(9) 0.0160(10)
O5 0.0260(12) 0.0351(12) 0.0278(12) 0.0130(10) 0.0061(9) 0.0085(10)
O6 0.0342(13) 0.0408(13) 0.0244(12) 0.0088(10) 0.0117(10) 0.0252(11)
O7 0.0430(14) 0.0275(12) 0.0262(12) 0.0138(10) 0.0209(11) 0.0185(10)
N1 0.0250(14) 0.0305(14) 0.0210(13) 0.0127(11) 0.0125(11) 0.0160(11)
C1 0.0326(18) 0.0306(17) 0.0283(17) 0.0165(14) 0.0164(14) 0.0131(15)
C2 0.0278(18) 0.0298(17) 0.0386(19) 0.0156(15) 0.0142(15) 0.0117(14)
C3 0.0317(19) 0.0262(17) 0.045(2) 0.0165(15) 0.0137(16) 0.0119(15)
C4 0.0299(19) 0.0327(18) 0.045(2) 0.0129(16) 0.0084(16) 0.0084(15)
C5 0.036(2) 0.037(2) 0.055(2) 0.0280(18) 0.0142(17) 0.0105(16)
C6 0.0260(16) 0.0243(15) 0.0235(16) 0.0094(13) 0.0147(13) 0.0144(13)
C7 0.0219(16) 0.0247(15) 0.0218(15) 0.0082(13) 0.0074(12) 0.0114(13)
C8 0.0248(16) 0.0223(15) 0.0230(16) 0.0105(13) 0.0075(13) 0.0119(13)
C9 0.0333(18) 0.0261(16) 0.0314(18) 0.0068(14) 0.0121(14) 0.0164(14)
C10 0.0350(19) 0.0170(15) 0.0390(19) 0.0083(14) 0.0126(15) 0.0101(14)
C11 0.0316(18) 0.0282(17) 0.0378(19) 0.0153(15) 0.0165(15) 0.0087(14)
C12 0.0299(18) 0.0255(16) 0.0289(17) 0.0106(14) 0.0147(14) 0.0146(14)
C13 0.035(2) 0.061(3) 0.048(2) 0.027(2) 0.0064(18) -0.0022(19)
C14 0.042(2) 0.041(2) 0.050(2) 0.0086(18) 0.0093(18) 0.0091(18)
C15 0.049(2) 0.045(2) 0.0269(19) 0.0017(16) 0.0055(16) 0.0245(18)
C16 0.066(3) 0.087(3) 0.030(2) 0.006(2) 0.0167(19) 0.054(3)

_geom_special_details            
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
P1 O1 1.468(2) . ?
P1 O2 1.572(2) . ?
P1 O3 1.587(2) . ?
P1 C6 1.816(3) . ?
P2 O4 1.475(2) . ?
P2 O6 1.565(2) . ?
P2 O5 1.575(2) . ?
P2 N1 1.623(3) . ?
O2 C1 1.465(3) . ?
O3 C3 1.461(4) . ?
O5 C13 1.454(4) . ?
O6 C15 1.458(4) . ?
O7 C8 1.360(3) . ?
N1 C6 1.470(3) . ?
C1 C2 1.525(4) . ?
C2 C3 1.519(4) . ?
C2 C5 1.533(4) . ?
C2 C4 1.534(4) . ?
C6 C7 1.525(4) . ?
C7 C12 1.391(4) . ?
C7 C8 1.399(4) . ?
C8 C9 1.396(4) . ?
C9 C10 1.396(4) . ?
C10 C11 1.382(4) . ?
C11 C12 1.394(4) . ?
C13 C14 1.464(5) . ?
C15 C16 1.507(5) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 P1 O2 111.67(12) . . ?
O1 P1 O3 111.28(13) . . ?
O2 P1 O3 106.27(11) . . ?
O1 P1 C6 112.81(13) . . ?
O2 P1 C6 108.08(14) . . ?
O3 P1 C6 106.36(13) . . ?
O4 P2 O6 116.97(13) . . ?
O4 P2 O5 108.81(13) . . ?
O6 P2 O5 101.44(13) . . ?
O4 P2 N1 112.83(13) . . ?
O6 P2 N1 104.85(13) . . ?
O5 P2 N1 111.39(14) . . ?
C1 O2 P1 119.88(18) . . ?
C3 O3 P1 119.58(19) . . ?
C13 O5 P2 120.5(2) . . ?
C15 O6 P2 123.0(2) . . ?
C6 N1 P2 124.0(2) . . ?
O2 C1 C2 111.3(2) . . ?
C3 C2 C1 108.0(2) . . ?
C3 C2 C5 108.9(3) . . ?
C1 C2 C5 108.4(3) . . ?
C3 C2 C4 110.3(3) . . ?
C1 C2 C4 110.7(3) . . ?
C5 C2 C4 110.5(3) . . ?
O3 C3 C2 111.5(2) . . ?
N1 C6 C7 113.6(2) . . ?
N1 C6 P1 107.3(2) . . ?
C7 C6 P1 111.33(19) . . ?
C12 C7 C8 118.6(3) . . ?
C12 C7 C6 121.8(3) . . ?
C8 C7 C6 119.6(2) . . ?
O7 C8 C9 121.9(3) . . ?
O7 C8 C7 117.5(3) . . ?
C9 C8 C7 120.5(3) . . ?
C8 C9 C10 120.1(3) . . ?
C11 C10 C9 119.5(3) . . ?
C10 C11 C12 120.4(3) . . ?
C7 C12 C11 120.9(3) . . ?
O5 C13 C14 109.7(3) . . ?
O6 C15 C16 107.6(3) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
O1 P1 O2 C1 158.0(2) . . . . ?
O3 P1 O2 C1 36.5(2) . . . . ?
C6 P1 O2 C1 -77.3(2) . . . . ?
O1 P1 O3 C3 -158.2(2) . . . . ?
O2 P1 O3 C3 -36.4(2) . . . . ?
C6 P1 O3 C3 78.5(2) . . . . ?
O4 P2 O5 C13 -179.1(3) . . . . ?
O6 P2 O5 C13 57.0(3) . . . . ?
N1 P2 O5 C13 -54.1(3) . . . . ?
O4 P2 O6 C15 67.6(3) . . . . ?
O5 P2 O6 C15 -174.2(2) . . . . ?
N1 P2 O6 C15 -58.2(3) . . . . ?
O4 P2 N1 C6 31.3(3) . . . . ?
O6 P2 N1 C6 159.7(2) . . . . ?
O5 P2 N1 C6 -91.4(2) . . . . ?
P1 O2 C1 C2 -51.5(3) . . . . ?
O2 C1 C2 C3 59.9(3) . . . . ?
O2 C1 C2 C5 177.8(2) . . . . ?
O2 C1 C2 C4 -61.0(3) . . . . ?
P1 O3 C3 C2 51.5(3) . . . . ?
C1 C2 C3 O3 -60.1(3) . . . . ?
C5 C2 C3 O3 -177.6(3) . . . . ?
C4 C2 C3 O3 61.0(3) . . . . ?
P2 N1 C6 C7 117.4(2) . . . . ?
P2 N1 C6 P1 -119.1(2) . . . . ?
O1 P1 C6 N1 -65.9(2) . . . . ?
O2 P1 C6 N1 170.16(17) . . . . ?
O3 P1 C6 N1 56.4(2) . . . . ?
O1 P1 C6 C7 59.1(2) . . . . ?
O2 P1 C6 C7 -64.9(2) . . . . ?
O3 P1 C6 C7 -178.68(18) . . . . ?
N1 C6 C7 C12 30.5(4) . . . . ?
P1 C6 C7 C12 -90.8(3) . . . . ?
N1 C6 C7 C8 -150.0(3) . . . . ?
P1 C6 C7 C8 88.7(3) . . . . ?
C12 C7 C8 O7 -179.5(3) . . . . ?
C6 C7 C8 O7 1.0(4) . . . . ?
C12 C7 C8 C9 -0.4(4) . . . . ?
C6 C7 C8 C9 -179.9(3) . . . . ?
O7 C8 C9 C10 179.7(3) . . . . ?
C7 C8 C9 C10 0.6(4) . . . . ?
C8 C9 C10 C11 0.0(5) . . . . ?
C9 C10 C11 C12 -0.8(5) . . . . ?
C8 C7 C12 C11 -0.4(4) . . . . ?
C6 C7 C12 C11 179.1(3) . . . . ?
C10 C11 C12 C7 1.0(5) . . . . ?
P2 O5 C13 C14 176.7(2) . . . . ?
P2 O6 C15 C16 153.5(2) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1 H1 O1 0.860(10) 1.950(11) 2.808(4) 176(3) 2_665
O7 H7 O4 0.90(4) 1.73(4) 2.624(3) 172(3) 2_666

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.327
_refine_diff_density_min         -0.424
_refine_diff_density_rms         0.065